Hot isostatic pressed pyrochlore glass-ceramics: Revealing structure insides at the reaction interface

As potential waste forms for immobilizing actinide-rich radioactive wastes, Eu₂Ti₂O₇ (Eu as a surrogate for minor actinides) pyrochlore glass-ceramics were fabricated via hot isostatic pressing (HIPing) at 1200°C. The structure and microstructure at the reaction interface between the glass-ceramic waste form and the stainless steel (SS) canister under HIPing conditions were carefully investigated with scanning electron microscopy (SEM), transmission electron microscopy (TEM), and synchrotron single crystal X-ray diffraction (SC-XRD). The interactions at the reaction interface led to the formations of a ~10-µm-thick Cr₂O₃ layer as the oxidation front of the SS and a layer of a mixed oxide phase (Eu_1.25SiCr_0.8Ti_1.2O_7.5) on the glass-ceramic side of the reaction interface. The crystal structure of such a unique mixed oxide phase was revealed indubitably with a combination of synchrotron SC-XRD and TEM assisted with a focused ion beam (FIB) SEM system. The improved structural understanding of the reaction interface will help to support the utilization of HIPing as a versatile hot consolidation process for the treatment of radioactive wastes.     

Reinforcing effect of nanocrystalline cellulose and office waste paper fibers on mechanical and thermal properties of poly (lactic acid) composites

Nanocrystalline cellulose (NCC) was prepared from office waste paper (OWP) by sulfuric acid hydrolysis method in this paper and it was used to prepare a series of poly (lactic acid) PLA/NCC composites by using a dissolution method in solvent N, N-dimethylformamide solution. The results indicated that with the addition of only 3 wt% NCC, the composites exhibited outstanding mechanical property. The tensile, bending and impact properties of the PLA/3NCC composite were improved by 8.2%, 13.1%, and 35.9% than those of pure PLA, respectively. On this basis, office waste paper fibers (OWF) were also used as a physical blended filler to enhance PLA/NCC composites to reduce the preparation cost of PLA composites and the perfect PLA/NCC/OWF sample was easily manufactured by melting–blending and injection molding. According to the crystallization and melting performance table, both NCC and OWF can act as nucleating agent to promote the crystallization properties on composites, while the blends did not have positive effect on thermal stability. Furthermore, the water absorption and degradation properties of PLA composites were also studied. This work not only provided a novel idea for the utilization of office waste paper but also successfully produced environment friendly composites with favorable mechanical properties and crystallization performance.     

A (4-fluorophenyl)(phenyl)phosphine oxide-modified epoxy resin with improved flame-retardancy,hydrophobicity, and dielectric properties

The compound (4-fluorophenyl)(phenyl) phosphine oxide (4-FPO) was designed, synthesized, and used in the modification of epoxy resin (EP). The 4-FPO-modified EP was prepared by curing the reaction mixture of diglycidyl ether of bisphenol A (DGEBA) and 4-FPO in the presence of 4,4′-diaminodiphenylsulfone (DDS). Compared with the unmodified EP, the limiting oxygen index value of the EP/4-FPO-0.6 (4-FPO-modified EP with 0.6 wt% of phosphorus) increased to 31.6%, and the sample achieved UL-94 V-0 rating. The peak of the heat release rate, average of the heat release rate, and total heat release of EP/4-FPO-0.6 were reduced by 39, 24, and 19%, respectively. Mechanism study showed that the quenching effect in the gas and barrier effect in the condensed phase were responsible for the enhanced flame-retardant properties of the 4-FPO-modified EP. The results showed that hydrophobicity and dielectric properties of the modified EP were clearly improved.     

Binary polymer blend of ArPTU/PI with advanced comprehensive dielectric properties and ultra-high thermally stability

Flexible high-temperature polymeric dielectrics with advanced dielectric properties are urgently demanded in various applications. In this work, series of polymer blend films were prepared from aromatic polythiourea (ArPTU) and polyimide (PI). The experimental results revealed that the blend films were properly engineered to achieve higher breakdown strength, greater dielectric constant, and larger energy density than pure PI film. For instance, the optimum property was obtained from the blend film with 10 wt% ArPTU, exhibiting prominent dielectric properties (K = 4.52, E_b = 443 MV/m), enhanced energy density (4.00 J/cm³) as well as excellent heat resistance (T_g = 419°C). In addition, stable dielectric properties at broad temperature range from −50 to 250°C were also acquired. It is deduced that the good compatibility from ArPTU and PI with similar polarity are responsible for the improved properties. The superior comprehensive properties which combine the advantages of ArPTU and PI suggest the potential applications of ArPTU/PI blend film in high-temperature dielectric areas.     

Synergistic improvement of mechanical and thermal properties in epoxy composites via polyimide microspheres

Achieving synergetic improvements of mechanical strength, toughness, and thermal stability of epoxy resin has been a crucial but very challenging issue. Herein, to explore a new solution for circumventing this issue, polyimide microspheres were successfully prepared through the inverse nonaqueous emulsion process, and the structure, size distribution and morphologies of polyimide (PI) microspheres were comprehensively investigated. Then the PI microspheres were incorporated in epoxy resin matrix to systematically investigate the mechanical and thermal properties of obtained epoxy/PI microspheres composites. It was found that the PI microspheres can not only enhance the mechanical strength of epoxy resin, but also significantly improve the toughness. Specially, the epoxy-based composites containing 3 wt% PI microspheres exhibit a 47% increase in tensile strength, while the G_IC and Charpy impact strength increase by 106% and 200%, respectively. The toughing mechanism of epoxy/PI microspheres composites was discussed. Moreover, the PI microspheres can also endow the epoxy resin with excellent thermal stability and heat resistance. Thus, this work may open a new opportunity to synergistically enhance the mechanical and thermal properties of epoxy-based composites and may also give some valuable inspiration for the rational design of other high-performance thermosetting composites.     

Effects of hydrolysis treatment on the structure and properties of semi-interpenetrating superabsorbent polymers

A semi-interpenetrating polymer network superabsorbent polymer based on sodium lignosulfonate-graft-poly(acrylic acid-acrylamide)/potassium dihydrogen phosphate and polyvinyl alcohol (PVA/SL-g-P[AA-AM]/KDP) was synthesized by using solution polymerization. The PVA/SL-g-P(AA-AM)/KDP was further hydrolyzed in NaOH solution. The structure, thermal stability, and morphologies of samples were examined by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The results of FTIR, TGA, and DSC showed that PVA interpenetration through SL-g-P(AA-AM)/KDP network has occurred, and PVA/SL-g-P(AA-AM)/KDP was successfully alkaline hydrolyzed. From the SEM images, the high porous and loose surface structure of polymers was formed after hydrolysis, which greatly increased the specific surface area. Samples after hydrolysis exhibited higher equilibrium swelling capacity (1963 g/g) compared to the nonhydrolyzed samples (866 g/g). The swelling kinetics of all samples well complied with the pseudo-second order swelling kinetics model. Simple hydrolysis treatment not only improved the swelling capacity of PVA/SL-g-P(AA-AM)/KDP but also induced an enhancement on its water retention performance, which made it potentially useful as a water retention agent in the revegetation of abandoned mines or slope wasteland.     

Enzymatic degradability and release properties of graphene oxide/silk fibroin nanocomposite films

The structure evolution of silk fibroin (SF) in the nanocomposite films with graphene oxide (GO) was investigated and related to the enzymatic degradability and release property. The interaction with GO was found to induce conformation transition of SF from random coil to β-sheet. However, the surface binding constrained the rearrangement of the silk chains, leading to a decrease of β-sheet when GO content was more than 1.0%. The crystal structure of SF played a key role in the degradation of GO/SF composites. The preferential degradation of the hydrophilic blocks resulted in a faster degradation of SF films with higher β-sheet content. The addition of GO to SF matrix led to a slower release and a reduction of the burst release of RhB, the model compound. The release profile was well fitted to the Rigter–Peppas equation, from which the characteristic constant decreased and the diffusional exponent increased with increasing GO content but quickly leveled off when GO content was more than 1.0%. Degradation of the composites had little influence on the characteristic constant of RhB release, however, led to an increased diffusional exponent, which was more evident for the composites with higher β-sheet content.     

Preparation and electrochemical application of an AgNW/graphene/SU-8 composite conductive photoresist

Photoresists play an increasingly important role in industrial fields like micro-electro mechanical systems, micromachining, and chip packaging. However, the traditional one-component photoresist is insulated, and additional steps are required to make it conductive, which complicates the process and limits its application. In order to solve the problem, we establish a one-step strategy to build conductive composite photoresist. Herein, graphene (GR) and silver nanowire (AgNW) are doped into SU-8 photoresist to fabricate a photo-patternable conductive composite. The composite photoresist is employed to make micro-patterns on an ITO electrode using photolithography, followed by electrochemical reduction of copper nanoparticles (CuNPs) to produce a nonenzymatic sensing coating. Experimental results prove that the response current of the obtained sensor is linearly related to the concentration of hydrogen peroxide in the range of 1–25 mM. The sensitivity and detection limit of the sensor are 41.8 μA mM⁻¹ cm⁻² and 9 μM, respectively. Moreover, excellent sensing performance including anti-interference, repeatability, and stability demonstrates the potential application of CuNPs/AgNW/GR/SU-8 composite material in electrochemical sensing.     

Engineering all-aromatic polyamide surface from hydrophilic to superhydrophobic and the accelerated strategy

Being a new kind of nanomaterials, aromatic polyamide nanofibers (ANF) have been much highlighted in recent studies. We here demonstrate an isopropyl alcohol (IPA) accelerated chemical cleavage on poly (p-phenylene terephthalamide) chopped fibers, which provides an efficient preparation method of ANF. The comprehensive study on the processes accelerated by different alcohols revealed that the preparation time of ANF in the mixed medium of dimethyl sulfoxide (DMSO)-alcohol (20:1 in volume) was shorten to 45 min and 75 min for methanol (ethanol) and isopropanol, respectively. However, the nanofibers prepared in DMSO-IPA exhibited the minimum in axial and radial dimensions, providing the finest and most uniform diameter of 16 nm. The corresponding ANF films through vacuum assisted filtration also showed the highest tensile strength of 150 MPa, in comparison with those of the ANF films prepared using other alcohols, which were about 110 MPa. Furthermore, ANF/silicon hybrid films were prepared by the ionic ring-opening reaction followed by the alkoxysilane condensation and nanoparticle fabrication. By changing the organo functional groups in the alkoxysilane, the surface of the films were adjustable in a wide contact angle range from 56° (hydrophilic) to 150° (superhydrophobic), suggesting the amendable interfacial properties potential applicable to composite fabrication with most of the resin matrix.     

Ultrahigh molecular weight polyethylene with improved crosslink density,oxidation stability,and microbial inhibition by chemical crosslinking and tea polyphenols for total joint replacements

Highly crosslinked ultrahigh molecular weight polyethylene (UHMWPE) stabilized by vitamin E (VE) is widely applied in artificial joints as the bearings. Despite the approval, there is a discord that VE lowers the crosslinking efficiency, limiting its use at high concentration. In this work, we aim to obtain highly crosslinked and oxidation resistant UHMWPE through the conjunction of tea polyphenol and chemical crosslinking. We hypothesized that highly incorporated tea polyphenol with multiple reactive sites can ameliorate crosslinking efficiency of chemical crosslinked UHMWPE in comparison to VE. Epigallocatechin gallate (EGCG) as representative tea polyphenol was incorporated into UHMWPE at high concentration (2–8 wt%), followed by chemical crosslinking with 2 wt% organic peroxide. Unlike VE/UHMWPE blends as the control, chemical crosslinking achieved an increasing trend in crosslink density of EGCG/UHMWPE blends with increasing antioxidant concentration. High concentration of EGCG also enhanced the oxidation stability of UHMWPE. Intriguingly, EGCG endowed UHMWPE with an excellent antimicrobial property, which was inefficient in VE/UHMWPE. Cell viability was hardly affected by the high loaded antioxidant and peroxide. The chemically crosslinked UHMWPE blended with EGCG is proved to be a reasonable, cost effective and realistic alternative for use in artificial joints.